JPS6366261A - Fire-retardant compound and thermoplastic composition containing the same - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to new and valuable flame retardant compounds, and in particular to thermoplastic compositions containing them. Furthermore, :T Specifically, the present invention provides brominated phthalimide 1. (a novel low-molecular polymer of polyal-1-lene oxide or a derivative derived therefrom, end-capped with
and its flame retardant combination with a normally IIJ flammable thermoplastic resin.

BACKGROUND OF THE INVENTION The use of certain additives to reduce the flammability of various thermoplastic polymers is well known to those skilled in the art. Flame retardant thermoplastic illumination compounds are desired in many areas of use such as building construction, automobile and aircraft manufacturing, packaging, electrical equipment, etc.

Many thermoplastics ignite at relatively low temperatures, and some have high ignition temperatures. Among the former, mention may be made of polystyrene, polyethylene, cellulose esters such as cellulose acetate and cellulose nitrate, and polyesters such as poly(ethylene terephthalate).

These are generally considered to be highly flammable.

On the other hand, some thermoplastics, such as aromatic polycarbonate, polyphenylene ether,
Polysulfones, polybenzimidazole, polyamides, etc. can be used at much higher temperatures than others, e.g. 700°F.
It will ignite if more than that. Even though these are not believed to be highly flammable, they still pose a potential hazard if they are not made flame retardant. For convenience, all of these resins are classified herein as "normally flammable." This is because, even though polycarbonate has a high ignition temperature, it ignites and supports two combustions every 20 seconds after the ignition source is removed, and particularly in thin samples, intense combustion is observed.

Therefore, it would be desirable to provide a composition that does not support combustion for more than a few seconds, even for highly flammable resins, but especially for resins with high ignition temperatures.

Many substances have been used as flame retardant additives in the technical field to make thermoplastics flame retardant. Many of these additives are halogen binding compounds, which are quite effective in achieving the desired results, but at the expense of some physical properties of parts molded from the compositions. However, increasing the amount of conventional halogenated flame retardant compounds often results in undesirable excessive i-+J plasticizing effects on normally rigid molded parts. In addition, especially in the case of thermoplastics with high ignition temperatures, there is a limit beyond which increasing the number of known flame retardant compounds no longer improves the flame-extinguishing properties of the composition. Finally, most conventional halogenated flame retardant compounds are somewhat volatile and "plate out" onto the surface of the molded article, reducing the desirable properties of the matrix polymer. This problem is particularly exacerbated with high ignition temperature thermoplastics such as polyesters and polyphenylene ethers alone or in combination with more impact resistant rubber modified polystyrene resins (HIPS). In these cases, processing is typically carried out at temperatures above about 200°C, at which temperatures conventional halogenated materials tend to plate out.

As a representative example of the current technological level, Fox (Fax)
U.S. Pat. No. 3,855,277 discloses flame retardants consisting of low molecular weight polymers of carbonates of halogenated dihydric phenols, alone or in combination with inorganic or organic antimony-containing compounds.

Sandler U.S. Patent No. 4,098
No. 704 discloses that poly(alkylene oxide) end-capped with tetrahalophthalate ester or tetrahalophthalate amide groups are useful for providing flame retardant properties to textiles. There is. In one example, tetrabromophthalic anhydride is reacted with di-primary amine end-capped polypropylene oxide to produce a co-1' acid-amide end-capped product.

However, this patent does not teach that any of these compounds function effectively as non-migrating internal flame retardants in thermoplastics.

U.S. Pat. No. 4,2 to Nevkirk et al.
No. 94.944 and No. 4,312,966, the reaction products of polyoxyalkylene compounds with halogenated aromatic diacids and anhydrides function as flame-retardant antistatic additives to polymer fibers. It is disclosed that However, in this special 1iQ, it is possible to use these additives in the form of a coating on the fiber surface to provide a softening effect, or to take advantage of the fact that these additives migrate to the surface and exhibit an antistatic effect. Although desirable, this rear point may be undesirable in three-dimensional molded parts, as already mentioned above.

Sand 1er U.S. Patent No. 4,39
No. 7゜977 discloses a flame retardant composition comprising a tetrahalophthalate plasticizer and a halogenated resin, in which the plasticizer is prepared by reacting tetrahalophthalate with a polyoxyalkylene compound or its amino derivative. It seems that it is made by In any case, these compounds are diesters or half acid esters, half acid amides or half ester amides. There is no disclosure of phthalimide end-capped units, nor is there any teaching that these plasticizers are non-migratory.

Halogenated flame retardants are also used in U.S. Pat. No. 4,433,088 to Haar et al.
I)01 In5), US Pat. No. 4,456,720. Ilaaf et al. disclose compositions using an aromatic bosphate, such as isopropylated triphenyl phosphate, and an adhesion promoter selected from polyolefin glycols and polyamides,
The composition is essentially polyolefin-free. The Abolins patent states that the use of halogenated organic compounds with boron-containing salts and esters that are stable at 250-300°C improves the flame retardancy of thermoplastic I11 compositions.

It is disclosed that

Triaryl phosphate and various ULs! Admixtures with t'iiJ plastic resins render thermoplastic compositions flame retardant, as disclosed in Axcl rod's U.S. Pat.
No. 526°917.

However, the halogenated and/or phosphorus-containing flame retardants used in the document No. 1 are particularly useful in thermoplastic compositions, in particular in polyphenylene ethers and high-impact polystyrene (1 When incorporated into plastic compositions, the flame retardant is still not completely 1 = row j/j electric.More specifically, flame retardants based on triaryl phosphates are can sometimes adversely affect the environmental stress cracking resistance of thermoplastic 11 resins.Increasing the molecular weight can reduce the volatility of this phosphate-containing flame retardant.
Even if an attempt is made to do so, the flame retardance tends to decrease, so it is not always successful.

Regarding the addition of halogenated materials such as brominated polycarbonates, brominated esters, and brominated polystyrene to thermoplastic compositions that are normally 11J flammable to render the compositions flame retardant, these The fuel is generally resin,
In particular, they are disadvantageous in that they are not compatible with polyphenylene ether resins, and as a result, the physical and heat-resistant properties of the blended compositions would be adversely affected.

Polyalkylene ether polymers and their derivatives of small molecules can be endowed with tetrabromophthalimide end groups, for example by reacting such polymers end-terminated with amino groups with tetrabromophthalic anhydride; It has been discovered that it is a very useful additive for flame retardancy. Additionally, the softening points of these small molecular products can be adjusted to suit the particular resin system in which they are incorporated.

Such products can be used alone or in combination with synergists such as phosphorus compounds to render normally flammable thermoplastic compositions flame retardant. Can be combined, especially with inorganic or organic antimony compounds.

For example, the molecular weight is between about 400 and about 2000, and the bromine content is about 5% by weight and 55%! 'i+, low molecular weight, tetrabromophthalimide-terminated poly(ethylene oxide) or poly(propylene oxide) or derivatives thereof, which melt below 200°C, are polyphenylene ether-styrene resin compositions. It is particularly advantageous for making objects flame retardant. Other polymers with 1:1 flammability include poly(
ethylene terephthalate), poly(butylene terephthalate), poly(bisphenol A carbonate) and acrylonitrile-butadiene-methyl non-terpolymer.

An antimony compound may also be contained at the same time.

Such compositions are "self-extinguishing," meaning they do not lose their ultimate physical properties and the additives do not plate out or volatilize during extrusion.
American Casualty Insurance Association Standards (Underwritersl, a)
Meets the stringent requirements of the 94 flammability test.

These additives also have a considerable plasticizing effect and have little tendency to excessively plasticize. This overcomes the main drawbacks of the current state of the art. Its flame retardancy is comparable to or better than that of triaryl phosphates, and there is no volatility problem.It has a flame retardancy comparable to that of brominated additives, but is not compatible with the often found incompatible additives. No problem.

It is therefore a principal object of the present invention to provide a family of highly efficient and novel low molecular weight polybrominated phthalimide end-capped poly(alkylene oxides) for use as flame retardants. be.

Another object of the present invention is to provide improved flame retardant polymer compositions containing low molecular weight flame retardant additives as described above.

Another object of the present invention is to provide a flame retardant composition in which the additive does not volatilize during molding or remains on the surface after molding.

Yet another object of the present invention is to provide a plasticized flame-retardant molding composition.

Other features and advantages of the present invention will become apparent from the detailed description below.

DESCRIPTION OF THE INVENTION According to the present invention, a flame retardant compound comprising polyalkylene oxide J or a derivative thereof terminal-capped with brominated phthalimide groups is provided.

This compound has the formula:

R-R1-←0-R1→-R(1) [R-RL+-0-Rl→-7NH-C-0(II) or [R-R1,000OR1+-7-CI(2-+-C- R2(
111) where R is r O and R1 is alkylene having about 2 to about 6 carbon atoms;
Preferably it is ethylene or propylene, R2 is alkyl of about 1 to about 6 atoms, and n is about 4 to about 4.
0, preferably about 5 to about 33, and n' is about 3 to about 1
5, preferably about 4 to about 8, particularly preferably about 5 to about 6
and n' is about 1 to about 10, preferably about 1.5 to about 2.5.

The present invention also includes flame retardant thermoplastic compositions comprising: (a) a normally flammable thermoplastic; and (b) (1
) a polyalkylene oxide compound of the above formula (1), (II) or (m) or a derivative thereof end-capped with a brominated phthalimide group; or (ii) the above compound (i) and an inorganic or organic antimony-containing compound. The combination with a compound consists of either a flame retardant amount.

In a preferred feature, compounds are selected in which R1 is a CH3-CH-CH2- group, in particular the following compounds are selected.

R-CHCH2〇-C112-CH→5-33R'C
H3C11g (R-CH-CH2+0-CH2-CH→〒page complete C1l
,,-)-CCII,, CI+3 where R is as described above.

In another preferred feature, the thermoplastic resin, usually with a +iJ flammability, is a polyphenylene ether or a mixture thereof with a polystyrene resin, a polymerization product of vinyl monomers, a polymerization product of olefin monomers, an acrylic monomer or a methacrylic monomer. It is selected from polymerization products, polymerization products of diene monomers, polyamides, cellulose esters, polyesters, aromatic polycarbonates, and mixtures of at least two of the above.

As a particularly preferable example, polyphenylene ether is poly(2,6-disubstituted-1,
4-phenylene ether) or poly(2゜6-dimethyl-1,4-phenylene-co-2,3゜6-drimethyl-1,4-phenylene ether) or a mixture of one or both of these, and the aromatic polycarbonate is poly(bisphenol-A carbonate!), the polyester is poly(1,4-butylene terephthalate), and the polymerization product of the allyl monomer is polybutadiene or a rubbery copolymer of styrene and butadiene with acrylonitrile and styrene. It is what it is.

DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "flammability-1" is used to mean that the resistance of the composition to flammability is significantly increased compared to a control sample. The most suitable method for directly measuring
(limiting oxygen index).

This test measures the flammability of a product based on the oxygen content of the combustion atmosphere. Place the appropriate specimen j1 in a combustion furnace and reduce the oxygen stepwise until the material no longer supports combustion. L
OI is expressed as the ratio (%) of nitrogen and oxygen in the gas used to burn the material in the test, divided by the ratio (%) of oxygen by 1, multiplied by 100. This oxygen index Test details are found in ASTM Test Method D-2863. Compositions of the invention incorporating specific types of flame retardant additives in specific amounts exhibit substantially higher oxygen indices than controls. , and therefore much less flammable.

Another useful criterion for determining flame retardancy is whether the quality of the composition is "non-flammable" or "self-extinguishing" as determined by the test specified in General Insurance Association Standard No. 94. It is to decide. In this test, after repeated ignition for 10 seconds with an exposed flame, the specimen was 5 to 30
If it self-extinguishes within seconds, the specimen is flame retardant.

The term "normal + iJ flammable thermoplastic resin" includes those that ignite at relatively low and relatively high temperatures. Wrapping items such as those generally described in the following. Exclude resins that are not normally flammable.

This is because such resins naturally contain or have been modified to contain elements such as halogens, phosphorous, large amounts of nitrogen, etc., which make them flame retardant. Because there is.

Not “normally flammable” and therefore composition of the invention = 2
4- Typical resins that are not included in the first resin component (a) of the product include polyvinyl chloride, polytetrafluoroethylene, chlorinated polyethylene, halogenated anhydride polyester, and halogen of polymer nails. Examples include aromatic polycarbonate 1.

For example, combustible thermoplastics typically include vinyl monomers, such as vinyl aromatics (styrene, vinyltoluene, vinylnaphthalene, vinylbenzene, mixtures thereof, etc.), vinyl esters (vinyl acetate, vinyl acetate, etc.) , polymerization products such as methylene methyl malonate, polymerization products of olefin monomers (e.g. ethylene, propylene, 1-butene, 2-butene, 1-decene, etc.) or dienes (e.g. butadiene, isoprene, etc.) [these and vinyl monomers] Synthetic acid (
acrylic or methacrylic monomers, such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid Polymerization products of isopropyl, n-butyl acrylate, t-butyl acrylate, hexyl acrylate and corresponding alkyl methacrylates, methyl allyl ketone, ethyl vinyl ether, diallyl ether, N-allyl caprolactam, N-allylacrylamide, etc. polymerization products of allyl monomers, unsaturated ketones such as methyl allyl ketone, polyamides such as adipic acid-hexamethylene diamine reaction products,
Cellulose esters such as cellulose acetate, cellulose acetate, cellulose nitrate, etc., aromatic polycarbonates such as phosgene-bisphenol-A reaction products,
Poly(2,6-dimethyl-1°4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene-two-2.3.6-drimethyl-1,4-phenylene ether) and poly(2, Polyphenylene ethers such as 6-diphenyl-1,4-phenylene ether)
1 as well as their combinations with styrene resins, polysulfones such as polyphenylene sulfone, polybenzimidazole, as well as wholly aromatic polyesters such as hydroquinone-terephthaloyl chloride reaction products, wholly aliphatic polyesters, etc. polyester, and
U.S.A.A'+ No. 2, 465.319 and No. 3,
Polyesters such as poly(alkylene iso and terephthalates), such as highly polymerized reaction products of glycols and esters of the corresponding phthalic acids, as described in US Pat.

In a particularly preferred embodiment of the invention, the normally combustible thermoplastic resin component is polyphenylene ether alone or in combination with styrene resin, aromatic polycarbonate-1, such as poly(bisphenol-A carbonate-1). ), polyesters, especially poly(alkylene terephthalates, isophthalates or mixed isophthalates)
terephthalates (the alkylene group has 2 to 10 carbon atoms A fi ), such as poly(ethylene terephthalate) or poly(1,4-butylene terephthalate),
Diene rubbers are copolymerization products of algenyl cyanide and vinyl aromatic compounds, such as butadiene or rubbery copolymers of styrene and butadiene, copolymerized with acrylonitrile and styrene. All such resins are widely commercially available and can be made by procedures known to those skilled in the art.

The low molecular weight M polymers of the present invention should and are preferably selected to provide flame retardancy along with plasticization. These materials can vary in molecular weight, % bromine content, and monomer structure. To optimally balance flame retardancy and plasticizing properties, it is desirable to minimize the polyalkylene chain length without simultaneously increasing the glass transition temperature. In any event, iiJ plasticity is easily tracked by flow channel measurements, and flammability is similarly easily tracked by standardized flammability tests, such as the Casualty Insurance Institute standard UL94 test.

The low molecular weight compounds of the present invention can be prepared by reacting polybromophthalic anhydride with a poly(alkylene oxide) or derivative thereof terminated with primary amine groups. This alkylene group has 6 carbon atoms
up to 3 alkylenes, such as ethylene, propylene,
It can be butylene, pentylene, hexylene, etc. groups, and the polyether group can be linear or branched.

The molecular weight of this product is a function of the number of repeating units in the polyether, typically 4-8 and 33 units being commercially available. However, a wide range of molecular weights is available.

Polyoxypropylene amine is manufactured by Texaco Chemical Company (
Texaco Chcmlcal Company under the trademark Jeffaminc, which is used for example by Jcl'
l'aIIIlno) Contains letters and numbers as part of it, such as D-4000.

The letters rDJ indicate that this compound has two primary amine groups in one molecule, and ITJ indicates that it has three amino groups in one molecule. Numbers represent average molecular weights.

To prepare compounds of formula (II), the corresponding primary amine end-capped polyalkylene oxide urea can be reacted with tetrabromophthalic anhydride. Such ureas can be obtained by reacting polyoxyalkylene amines with phosgene or its equivalent urea, diphenyl carbonate, etc., and are available from Texaco.
Chemical i1. (Texaco Cl+emical
Company) is commercially available under the trade name DU700■.

As already mentioned, the use of low molecular weight additives (b)(i) in combination with synergists is a preferred feature of the invention. Suitable synergists include inorganic and organic antimony compounds. Such compounds are widely available or can be produced by known methods. The type of antimony compound used is not critical; the choice is primarily based on economics. For example, inorganic compounds include antimony oxide (Sb203), antimony phosphate, KSb (OH), NH SbF6, Sb
You can use something like 83. A wide variety of organic antimony compounds can also be used, including antimony esters with organic acids, cyclic alkyl antimonites, aryl antimonic acids, and the like. Examples of organic antimony compounds including inorganic salts of the compound include tartaric acid K S b
, caproic acid Sb, Sb (OCH,, CH3) 3
．． 5t) (OCR(CH2)CH2CH3)3, polymethylene glycolic acid sb, triphenylantimony, etc. Particularly preferred is antimony oxide.

■ The low molecular weight polyether or its derivative end-capped with a halogenated phthalimide used as a flame retardant additive is not critical to the present invention, but In small proportions (if used in large quantities it is uneconomical and may impair the physical properties), at least in some cases to make thermoplastic resins flame retardant, non-flammable or self-extinguishing. It is well recognized by those skilled in the art that this will vary depending on the nature of the combustible thermoplastic and the relative efficiency of the additives. In general, the poison of additives is 0 per 100 parts by weight of the resinous component (a).
, 5 to 50 parts by weight, and if the amount is small, the flame retardance is 1!
7, and a larger amount is used to make it self-extinguishing. A preferred range is about 1.0 to 30 parts of the additive per 100 parts by weight of resinous component (a), and a particularly preferred range is about 5 parts by weight of the additive.
~about 25 parts. Compounds that are highly enriched in bromine may require smaller amounts. For example, n or n'
If n is 7, a larger amount will be needed than if n or n' is 3 or 4. Although the amount of antimony compounds can vary over a fairly wide range, it is generally expressed as antimony oxide and contains thermoplastic resinous component (a) 1
From about 0.5 to about 20 parts by weight per 0.00 parts, preferably from about 1 to about 10 parts by weight of antimony oxide. Other antimony compounds can also be used in corresponding equivalent molar amounts. In the combination of antimony and poly(ether-halogenated phthalimide) within the scope of this invention, the weight ratios in this combination can vary widely, but for each 1.0 parts by weight of the low molecular weight polymer additive component. It is preferred to use about 0.1 to 1.0 parts of antimony compound.

In the composition of the present invention, a filler, a reinforcing agent, a 1 liter type agent,
The inclusion of other ingredients such as pigments, stabilizers, nucleating agents, etc. in amounts conventional for the purposes for which they are commonly used is also considered to be a feature of the invention.

The manner in which flame retardant additives are added to the thermoplastic resin (and any reinforcing agents that may be present) is not critical, is conventional, and will be obvious to those skilled in the art. However, it is possible to add each component as part of a blend premix and mix this, for example by passing it through an extruder or coalescing on a mill at a temperature depending on the needs of the particular composition. preferable. The mixed composition can be cooled and cut into moldable particles, which can be molded into a mold or extruded to give a desired shape.

It should be understood that the compositions of the present invention can be used in many different final forms.

For example, they can be molded into three-dimensional articles, formed into films, or formed into fibers by conventional techniques.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate and describe the preparation of some compounds and compositions within the scope of this invention. They are not considered to limit the scope of the invention in any way.

Example 1 Tetrabromophthalic anhydride and polyoxypropylene diamine [Texaco Chemical Co. (Tc
A product manufactured by xaco Cbcmcal Co. under the trademark Chefamine CJerramineO) D 2000] is added in a molar ratio of 2=1. This flask is used for approximately 3 c/g of reactant to allow foaming.
It has a capacity of c. The flask containing these reactants is placed in an oil bath under some nitrogen atmosphere.

Heat the oil bath to approximately 160-180°C and begin stirring as soon as the solids are sufficiently dissolved. Most of the water is removed within the first 30 minutes of heating and the reaction is complete after about 2-3 u total stirring for 17 hours. Cool the product. This product is a waxy substance. Use this as is.

The bromine content is 22% by weight.

Example 2 Polyoxypropylene diamine with a molecule m of about 400 [Jcframlno' D 40
0] and repeat the procedure of Example 1. The product is 14
It melts at 6°C and has a bromine content of about 50% by weight.

Example 3 Poly(oxyethylene) diamine with a molecular weight of about 900 [
Chef Amin (JefTamlnc”) ED 90
Repeat the procedure of Example 1, substituting 0 ]. The product has a melting point of approximately 80°C and a bromine content of approximately 35% by weight.

Example 4 Di(aminopolyoxypropylene) with a molecular weight of about 700
Urea [JcffamlnaO] D U
Repeat the procedure of Example 1 using 700] instead.

The product melts at approximately 125°C and has a bromine content of approximately 37% by weight.

Example 5 Polyoxypropylenetriamine [Chefamine (Jcffa
Repeat the procedure of Example 1 using mlnaO)T403] instead. The product melts at approximately 80°C and has a bromine content of approximately 53% by weight.

Example 6 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene ether), 50 parts by weight of polybutadiene-modified polystyrene, 15° of the etherimide of Example 2 having the following formula: A composition is prepared consisting of 0 parts by weight, 0.15 parts by weight each of zinc sulfide and zinc oxide, and 1 part of 3.24 parts of antimony oxide. Blend the ingredients listed in the book in a Waring blender, and use a 28mm+ Werner Bufreiderer (V
Extrude in a stock temperature of 600'F under atmospheric pressure in a ernet Pl'eldercr) extruder. Next, the extruded pellets were added to 4 ounces of Newberry (N
ewberry) injection molding machine (nozzle, front and back all 505'l'', mold 150°) to form standard test bars. Various properties of this composition have been publicly recognized. Test according to the test method.The results are shown in Table 1 below.
(described after Comparative Examples 8 to 13 below).

Example 7 The procedure of Example 6 is followed using the same starting materials.

However, instead of the etherimide of Example 2, the urea of Example 4 with the following formula: % formula % (where R is tetrabromophthalimide) is used, and the antimony oxide is 2.4
Reduce to 5 parts by weight. The results are shown in Table 1 below (Comparative Examples 8-
(described after 13). As shown in Table 1,
Examples 6 and 7 of the present invention exhibit excellent flame retardant properties, as well as excellent tensile strength and flexural strength.

Comparative Examples 8 to 13 Six types of compositions are prepared in the same manner as in Examples 6 and 7 for comparison. However, the following flame retardant was used instead of the etherimide compound used in Examples 6 and 7.

Comparative Example 8 Nigerate Lakes Co., Ltd. (Great L, akes C
Poly(dipromostyrene) manufactured by Orporatlon
4.5 parts by weight of homopolymer and 1.44 parts by weight of antimony oxide.

Comparative Example 9: 10.7 parts by weight of poly(dipromostyrene) and 3.24 parts by weight of antimony oxide.

Comparative Example 10: 7.5 parts by weight of poly(dipromostyrene) and 2.45 parts by weight of antimony oxide.

Comparative Example 11: PMC Corporation
KRONITEX 7, (KRONITEX) 500
15.0 parts by weight of isopropylated triphenyl phosphate sold by Tou Sho + Fite.

Comparative Example 12: 15.0 parts by weight of a flame retardant current plasticizer. This is 1,3
and 1,4-butylene 0-phthalate (sold under the trademark Nuodcx Corporation or AI MIEX 433 B).

Comparative example 13: No flame retardant additives.

Various properties of these compositions were tested. The results are shown in Table 1 below.

As can be readily seen from Table 1, the novel flame retardants of the present invention have superior tensile strength and flexural strength compared to prior art flame retardants. As already pointed out, the flame retardants of the invention have better compatibility with thermoplastics than conventional brominated flame retardants (Example 6 and Comparative Example 9* and Example 7 and Comparative Example 10* (Compare).

Example 14 Poly(1,4-butylene terephthalate) resin [General Electric Co. (Goncral I; 1oet
rIe Go, ) (7) Barox (■Al, Ox■
) 315], 440 parts by weight of the flame retardant compound of Example 3 of the present invention, and 13 parts by weight of antimony oxide.
0 parts by weight were blended and the temperature was adjusted to 450.480.500.
3' Sterling 1- set at 500°F.
ing) Extruded with an extruder. This blend was injection molded into test parts. The properties were as follows.

Notch;] Izot impact strength 1/8' 0, 6 ft, 1
bs,/In.

Tensile Strength 6700 psi Tensile Elongation 114% Flammability Rating LT L 94 V-0 The following may be substituted to make the flame retardant compositions of the present invention.

Thermoplastic resins include poly(ethylene terephthalate), poly(bisphenol-A carbonate), acrylonitrile-butadiene-styrene (ABS) terpolymer, or poly(2,6-dimethyl-1,4-phenylene-co-2. 3°6-drimethyl-1,4-phenylene ether) resin can be used.

A fibrous glass reinforcement may be added to the composition of Example 6, in an amount such that 30 parts by weight of glass per 100 parts by weight of glass, Borif J-nylene ether and high impact rubber modified polystyrene. shall be sufficient to make 1 part.

-42 - In the compositions of Examples 6 and 7, stoichiometric amounts of triphenylantimony, thorium antimonite and 5b(OCH2CHa)a may be used in place of antimony oxide.

Compositions comprising polyphenylene ethers or mixtures thereof with styrenic resins in embodiments disclosed herein are disclosed in Llay U.S. Pat.
74 and 3,306,875 and Cizek, US Pat. No. 3,383,435. A particularly preferred composition consists of a mixture of 25 to 75 parts by weight polyphenylene ether and 75 to 25 parts by weight styrene resin.

The styrenic resin has at least 25% by weight of one polymer unit derived from a compound of the formula:

Here, R2 is hydrogen, (lower) alkyl or norogen, Z is selected from 11 groups consisting of vinyl, hydrogen, chlorine and (lower) alkyl, and p is from 0 to 5. are equal integers.

As used herein and in the claims, the term ``styrenic resin'' as defined by the formula ``1'' includes, for example, homopolymers such as polystyrene, rubber-modified polystyrene, etc. Modified polystyrene and styrene-acrylonitrile copolymer (SAN)
, styrene-butadiene copolymer, styrene-acryloni], crew α-alkyl-styrene copolymer, styrene-acrylonitrile-butadiene copolymer (A
BS), poly-α-methylstyrene, copolymers of ethylvinylbenzene and divinylbenzene, and the like. Preferred styrenic resins are high impact polystyrene, ABS copolymers and SAN copolymers.

Although the embodiments described above are illustrative of various modifications of the invention, other modifications are possible in light of the above teachings. It is therefore to be understood that various modifications may be made to the specific embodiments of the two series within the scope of the invention as defined in the claims.

Claims (20)

[Claims] (1) Consisting of polyalkylene oxide or its derivatives end-capped with brominated phthalimide groups, formula: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 is alkylene with about 2 to about 6 carbon atoms, R^2 is alkyl of about 1 to about 6 carbon atoms, n is about 4 to about 40, n' is about 3 to about 15, and n'' is about 1 to about 10] A flame retardant compound represented by (2) A compound of formula (I) according to claim 1, wherein n is about 5 to about 33. (3) A compound of formula (II) according to claim 1, wherein n' is about 4 to about 8. (4) The compound of formula (III) according to claim 1, wherein n'' is from about 1.5 to about 2.5. (5) The compound according to claim 1, wherein R^1 is ethylene or propylene. (6) The compound according to claim 5, wherein R^1 is a ▲ group, which includes a mathematical formula, a chemical formula, a table, etc. (7) The above compound: ▲ has a mathematical formula, chemical formula, table, etc. ▼, ▲ has a mathematical formula, chemical formula, table, etc. ▼, or ▲ has a mathematical formula, chemical formula, table, etc. ▼ [However, R stands for ▲ mathematical formula, chemical formula, table, etc. The compound according to claim 6, characterized in that the compound is selected from ▼. (8) (a) usually a flammable thermoplastic resin, and (b) an effective flame retardant amount, (i) end-capped with a brominated phthalimide group, with the formula: ▲Mathematical formula, chemical formula, table, etc. ▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^1 is alkylene of about 2 to about 6 carbon atoms, R^2 is alkyl of about 1 to about 6 carbon atoms, n is about 4 to about 40, and n' is about 3 to about 15, and n'' is about 1 to about 10], or (ii) a compound of the formula (I), (II) or (III) or their A flame-retardant thermoplastic composition comprising any mixture and combination of an inorganic or organic antimony-containing compound. (9) The flame-retardant thermoplastic composition according to claim 8, wherein n in formula (I) is about 5 to about 33. (10) The flame-retardant thermoplastic composition according to claim 8, wherein n' in formula (II) is about 4 to about 8. (11) The flame-retardant thermoplastic composition according to claim 8, wherein n'' in formula (III) is from about 1.5 to about 2.5. (12) The flame-retardant thermoplastic composition according to claim 8, which is R^1 ethylene or propylene. (13) The flame-retardant thermoplastic composition according to claim 12, wherein R^1 is a ▲ group, which includes a mathematical formula, a chemical formula, a table, etc. (14) The above compound: ▲ has a mathematical formula, chemical formula, table, etc. ▼, ▲ has a mathematical formula, chemical formula, table, etc. ▼, or ▲ has a mathematical formula, chemical formula, table, etc. ▼ [However, R stands for ▲ mathematical formula, chemical formula, table, etc. The flame-retardant thermoplastic composition according to claim 9, characterized in that the composition is selected from the following. (15) The flame-retardant thermoplastic composition according to claim 8, wherein the antimony-containing compound is antimony oxide. (16) A flame-retardant thermoplastic composition according to claim 8, characterized in that it also contains a flame retardant different from the flame retardant defined for component (b)(i). (17) The usually flammable thermoplastic resin is polyphenylene ether or a mixture thereof with a polystyrene resin, a polymerization product of vinyl monomers, a polymerization product of olefin monomers, a polymerization product of acrylic or methacrylic monomers, a diene. Flame-retardant thermoplastic composition according to claim 8, characterized in that it is selected from polymerization products of monomers, polyamides, cellulose esters, polyesters, aromatic polycarbonates, or any mixtures of the above. thing. (18) The polyphenylene ether is poly(2,6-
dimethyl-1,4-phenylene)ether or poly(2,6-dimethyl-1,4-phenylene-co-2,3)
, 6-trimethyl-1,4-phenylene ether) or a mixture of both. (19) The flame-retardant thermoplastic composition according to claim 17, wherein the aromatic polycarbonate is poly(bisphenol-A carbonate). (20) A flame-retardant thermal flame retardant according to claim 17, characterized in that the polymerization product of the diene monomer consists of polybutadiene or a rubbery copolymer of styrene and butadiene and acrylonitrile and styrene. Plastic composition.